US9035169B2 - Layered compound-metal particle composite and production method therefor, and suspension, film and flexible solar cell using same - Google Patents
Layered compound-metal particle composite and production method therefor, and suspension, film and flexible solar cell using same Download PDFInfo
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- US9035169B2 US9035169B2 US13/985,193 US201213985193A US9035169B2 US 9035169 B2 US9035169 B2 US 9035169B2 US 201213985193 A US201213985193 A US 201213985193A US 9035169 B2 US9035169 B2 US 9035169B2
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- United States
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- layered compound
- metal particle
- particle composite
- metal
- composite
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- 239000002923 metal particle Substances 0.000 title claims abstract description 121
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 83
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- 238000009830 intercalation Methods 0.000 claims abstract description 11
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- 238000000034 method Methods 0.000 claims description 41
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- 239000010931 gold Substances 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 24
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
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- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- B22F1/0018—
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B82—NANOTECHNOLOGY
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01B33/00—Silicon; Compounds thereof
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- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2006/40—Electric properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
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- C09C3/041—Grinding
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/256—Heavy metal or aluminum or compound thereof
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Definitions
- the present invention relates to a layered compound-metal particle composite and to a method of producing such a composite.
- the invention further relates to a layered compound-metal particle composite suspension and to a layered compound-metal particle composite thin-film and a flexible solar cell using the same.
- Patent Document 1 discloses technology in which a composite obtained by causing precious metal nanoparticles to aggregate within a fluid matrix such as smectite and stabilizing the aggregated state is used as a surface-enhanced Raman scattering (SERS) matrix in Raman spectroscopy that employs surface-enhancing Raman scattering.
- SERS surface-enhanced Raman scattering
- Known methods for producing such composites includes the techniques of obtaining a composite sol (composite) of fine precious metal particles and fine plate-like particles by inducing the formation of fine precious metal particles within a dispersion of fine plate-like particles of smectite or the like dispersed in an aqueous solution or a highly polar solvent (see Patent Documents 2 and 3).
- Patent Document 1 Japanese Patent Application Laid-open No. 2006-184247
- Patent Document 2 Japanese Patent Application Laid-open No. H11-61209
- Patent Document 3 Japanese Patent Application Laid-open No. H10-182142
- montmorillonite group minerals which are a leading type of clay-based layered compounds, have a layered structure created by the repetition of a three-layer structure in which a regular octahedron serves as the basic skeleton, and contain alkali metal ions as exchangeable anions between the layers.
- montmorillonite group minerals are generally hydrophilic at the surface and between the layers, they have an excellent affinity to highly polar substances such as water, dimethyl formamide and other polar solvents. On the other hand, they lack affinity with low-polarity substances such as toluene, ketone-type solvents and other solvents having a low polarity.
- a layered compound-metal particle composite is dispersed in the bulk heterolayer of an organic solar cell, and the photoelectric conversion ratio is enhanced by the plasmonic functionality of the metal nanoparticles
- the metal nanoparticles if there is no affinity between the organic semiconductor making up the bulk heterolayer and the layered compound-metal particle composite, the metal nanoparticles have difficulty approaching the bulk heterojunctions, making an adequate photoelectric conversion-improving effect impossible to obtain. Accordingly, introducing layered compound-metal particle composites obtained by the methods of Patent Documents 2 and 3 into the bulk heterolayer of an organic solar cell for the sake of improving photoelectric conversion is difficult.
- a further object is to provide a method of manufacturing such a composite.
- Still further objects are to provide a coating, an applied coat, and an electronic device and a photoelectric conversion device, as well as a method for controlling the performances thereof, all of which entail the use of such a composite.
- Patent Documents 2 and 3 The inventors initially attempted to apply the techniques of Patent Documents 2 and 3 for producing a layered compound-metal particle composite within a homogeneous liquid phase using an aqueous solution or a highly polar solvent in order to create a composite of an organically modified layered compound lipophilized by the intercalation of organic ions and a metal colloid within a homogeneous phase composed of a nonaqueous solvent.
- a layered compound-metal particle composite having an excellent affinity to low-polarity substances can be obtained by adding, to an organically modified layered compound that has been lipophilized by the intercalation of organic ions, an aqueous colloidal metal solution and a nonaqueous solvent which is a poor solvent for the metal colloid and has an excellent ability to swell the organically modified layered compound.
- the inventors have found that when a nonaqueous solvent having such a low polarity as to be incompatible with water is used, although the aqueous phase within which the metal colloid is dispersed and the organic phase (nonaqueous solvent) within which the organically modified layered compound is dispersed enter into a phase-separated state, surprisingly, formation of a composite of the metal colloid and the organically modified layered compound proceeds at the interface between the aqueous phase and the organic phase, and the resulting composite moves into the organic phase.
- the organically modified layered compound due to the intercalation of organic ions, is modified so as to become hydrophobic and also acquires from the organic ions an excessive charge at the surface and between layers.
- the metal colloid contained within the aqueous colloidal metal solution is generally surface-modified with citric acid or the like to increase its affinity to water.
- the surface of the metal colloid depending on the place, exhibits hydrophobic properties inherent to the metal particles, or exhibits hydrophilic properties owing to hydrophilic groups on the surface modifier.
- hydrophobic interactions or electrostatic interactions occur between the metal colloid and the organically modified layered compound, leading to the formation of a composite of the metal colloid and the organically modified layered compound.
- the inventive method of producing a layered compound-metal particle composite is a method of producing a composite of a layered compound and metal particles which is characterized by including the steps of: forming an organically modified layered compound by intercalating organic ions between layers of the layered compound; and adding to the organically modified layered compound an aqueous colloidal metal solution in which the metal particles are dispersed as a metal colloid in water and a nonaqueous solvent which is a poor solvent for the metal colloid and has an excellent ability to swell the organically modified layered compound.
- the nonaqueous solvent has a solubility parameter (SP) difference with the metal colloid of preferably at least 9 MPa 1/2 , more preferably at least 13 Pa 1/2 , and even more preferably at least 21 MPa 1/2 .
- SP solubility parameter
- the formation of a composite between the organically modified layered compound and the metal colloid can be more reliability made to proceed.
- the frequency of contact between the metal colloid having a high affinity to water and the organically modified layered compound having a high affinity to nonaqueous solvents is increased, enabling the formation of a composite of the metal colloid and the organically modified layered compound to be promoted.
- the nonaqueous solvent it is preferable for the nonaqueous solvent to have a lower dielectric constant than the amphiphatic solvent.
- the metal particles may include at least one from among gold, silver, copper, aluminum and platinum.
- organic cations or organic anions of any structure may be used as the organic ions. More specifically, the organic ions may be of at least one type from among sparingly water-soluble or water-insoluble quaternary ammonium salts, phosphonium salts, fluorescent cationic dyes and oxonium salts.
- the layered compound is not particularly limited, provided it is a layered compound having exchangeable ions between the layers.
- a layered clay compound belonging to the montmorillonite group of minerals or the mica group may be used.
- the layered compound-metal particle composite according to the invention is characterized by being obtained by the above-described production method.
- the layered compound-metal particle composite obtained by the above production method has an excellent affinity to low-polarity substances, when dispersed in a low-polarity solvent of excellent volatility to form a paste, it can be incorporated into a desired device through the use of a film-forming method of excellent work efficiency and economy, such as printing or coating. Moreover, because it has an excellent affinity to low-polarity substances, this layered compound-metal particle composite can be combined with an organic substance to obtain devices having a variety of functions.
- the layered compound-metal particle composite suspension according to the invention is characterized by including the above-described layered compound-metal particle composite and an organic solvent as a dispersion medium for the layered compound-metal particle composite.
- the organic solvent used as the dispersion medium may be the “nonaqueous solvent” that was used when forming the above layered compound-metal particle composite.
- the above layered compound-metal particle composite suspension may further include at least one from among an organic dye, a hole transporting material, a p-type semiconductive material, an electron transporting material, an n-type semiconductive material and a crosslinkable material.
- an organic dye By including an organic dye, a hole transporting material, a p-type semiconductive material, an electron transporting material or an n-type semiconductive material in the suspension, it is possible to form functional films having various functionalities. And by including a crosslinkable material, the strength of the functional film that has been formed can be enhanced.
- the layered compound-metal particle composite thin-film of the invention is characterized in that it is obtained by coating a surface thereof with the above layered compound-metal particle composite suspension.
- the layered compound-metal particle composite multilayer functional film of the invention is characterized by being composed of a stack of layers which include a plurality of the layered compound-metal particle composite thin-films, the plurality of layered compound-metal particle composite thin films having mutually differing properties.
- the above layered compound-metal particle composite multilayer functional film may include an insulating layer composed of a layered compound-metal particle composite thin-film having a surface resistance of at least 100 k ⁇ /, a pair of dielectric layers composed of layered compound-metal particle composite thin-films having a surface resistance of at least 1 k ⁇ / but less than 100 k ⁇ / and disposed, respectively, on a surface side and a back side of the insulating layer, and current-collecting electrode layers composed of layered compound-metal particle composite thin-films having a surface resistance of not more than 10 ⁇ / and disposed as surfacemost layers.
- the multilayer functional film as a whole manifests the functionality of a capacitor.
- an electrolytic solution containing an electrolyte use as an electrical double layer type capacitor (a large-capacity capacitor) is also possible.
- a dye for photoelectric conversion may be added to one of the current-collecting electrode layers and a layer adjacent thereto. In this case, use as a novel light-inducible electrical double-layer type capacitor is possible.
- the layered compound-metal particle composite multilayer functional film can thereby be utilized in devices which employ the phenomenon of photoelectric conversion, such as solar cells and water photolysis devices.
- an electron acceptor that is photoreduced by the dye may be added to the insulating layer (the insulating layer provided between the polarizable electrodes) or to the insulating layer and the dielectric layers.
- the layered compound-metal particle composite multilayer functional film may have a symmetrical layered structure divided by the insulating layer, and may have added thereto two photoelectric conversion dyes having spectral sensitivities or light absorption wavelength maxima mutually differing by at least 20 nm, one dye being added to one of the current-collecting electrode layers and a layer adjacent thereto, and the other dye being added to the other current-collecting electrode layer and a layer adjacent thereto.
- the layered compound-metal particle composite multilayer functional film stacked on one side of the insulating layer may include platinum particles as the metal particles, and the layered compound-metal particle composite multilayer functional film stacked on the other side of the insulating layer may include particles of at least one of gold, silver, copper and aluminum.
- the flexible solar cell according to the invention may have a first electrode which is a dielectric layer or a solid electrolyte layer composed of the above-described layered compound-metal particle composite multilayer functional film and has a metal particle content of less than 50 wt %, and a second electrode which is a carbon fiber electrode. That is, in order to have one electrode with the plasmon enhancing effect of metal particles function as a light input side electrode, it is not always necessary to have the other electrode be light transmitting. It is thus possible to deliberately introduce electrode materials in which properties such as low cost, flexibility and electrical conductivity have been improved to at least the same level as in the conventional art. Such electrode materials are exemplified by carbon fiber electrodes.
- two electrodes composed of the above-described layered compound-metal particle composite of the invention having different light transmittances can be used in an arrangement that includes a dielectric layer or a solid electrolyte therebetween.
- the inventive composite a paste which is a high-concentration dispersion thereof, and a thin film and a stacked structure of two or more thin-films formed from the paste are characterized by being composed of metal particles and an inorganic material or an inorganic-organic hybrid compound that adsorbs the metal particles and being able to maintain a dispersed state within a nonaqueous solvent.
- the electrical conductivities, plasmon resonances or optical absorption characteristics thereof are controlled in accordance with the content and degree of aggregation of the metal particles.
- This invention by using a nonaqueous solvent which is a poor solvent for metal colloid and has an excellent ability to swell organically-modified layered compound, is able to bring about the formation of a composite of an organically modified layered compound that has been lipophilized by the intercalation of organic ions and the metal colloid in an aqueous colloidal metal solution. As a result, a layered compound-metal particle composite having excellent affinity with low-polarity substances is obtained.
- FIG. 1 is a diagram showing the method of producing a layered compound-metal particle composite according to a first embodiment of the invention.
- FIG. 2 is a diagram showing the method of producing a layered compound-metal particle composite according to second embodiment of the invention.
- FIG. 3 is a graph showing the transmission/absorption spectrum measured for the aqueous metal nanocolloid solution in Example 1.
- FIG. 4 is a photograph showing the manner in which a gold colloid moved from an aqueous phase into an organic phase in Example 1.
- FIG. 5 is a graph showing the FT-IR spectrum measured for the red-violet residue in Example 1.
- FIG. 6 is a transmission electron micrograph showing the gold nanoparticles in Example 2.
- FIG. 7 is a graph showing the absorption spectrum measured for the organic phase in Example 3.
- FIG. 8 is a graph showing the absorption spectrum measured for the film produced in Example 4.
- FIG. 9 is a graph showing the FT-IR spectrum measured for the colored powder obtained in Example 6.
- FIG. 10 is a diagram showing the construction of the electrical double-layer capacitor produced in Example 11.
- FIG. 11 is a diagram showing the construction of the photocapacitor having a 5-layer structure produced in Example 13.
- FIG. 12 is a diagram showing the construction of the film-type solar cell produced in Example 14.
- FIG. 13 is a diagram showing the construction of the water photolysis device produced in Example 15.
- FIG. 14 is a diagram showing the construction of the reaction cell used in Example 15.
- FIG. 15 is a diagram showing the construction of an experimental apparatus for observing Raman scattering in Example 16.
- FIG. 16 is a graph showing the results of Raman scattering observations in Example 16.
- FIG. 17 is a table showing the relationship between the composite formation conditions and the composite forming phenomena for the working examples and comparative examples in which layered compound-metal particles composites were produced.
- FIG. 1 is a diagram showing the method of producing a layered compound-metal particle composite according to the first embodiment.
- an aqueous colloidal metal solution 2 and a nonaqueous solvent are added to an organically modified layered compound 1 which has been lipophilized by the intercalation of organic ions between the layers, thereby forming a layered compound-metal particle composite 3 having an excellent affinity with low-polarity substances.
- the layered compound prior to lipophilization of the organically modified layered compound 1 is not particularly limited, provided it is a layered compound having exchangeable ions between the layers.
- layered clay compounds belonging to the montmorillonite group of minerals or the mica group may be advantageously used.
- the montmorillonite group of minerals are clay minerals of the following general formula (X,Y) 2-3 Z 4 O 10 (OH) 2 .mH 2 O.(W 1/3 ) (wherein X is Al, Fe(III), Mn(III) or Cn(III); Y is Mg, Fe(II), Mn(II), Ni, Zn or Li; Z is Si or Al; W is K, Na or Ca; H 2 O is interlayer water; and m is an integer).
- X and Y various compounds, including montmorillonite, magnesian montmorillonite, iron montmorillonite, iron magnesian montmorillonite, beidellite, aluminian beidellite, nontronite, aluminian nontronite, saponite, aluminian saponite, hectorite and sorconite, exist as natural products.
- synthetic products in which OH groups within the above formula are substituted with halogens such as fluorine are also commercially available. Any of these may be used.
- Organic cations or organic anions of any structure may be used as the organic ions for lipophilizing the organically modified layered compound 1 , and are exemplified by onium salts such as quaternary ammonium salts, phosphonium salts, fluorescent cation dyes or oxonium salts which are sparingly soluble or insoluble in water. More specifically, preferred use may be made of quaternary ammonium salts having bulky cations with four alkyl groups of four or more carbons, phosphonium salts having bulky cations such as alkylphosphonium ions and arylphosphonium ions, and oxonium salts having bulky cations as counterions of perchlorate anions.
- onium salts such as quaternary ammonium salts, phosphonium salts, fluorescent cation dyes or oxonium salts which are sparingly soluble or insoluble in water. More specifically, preferred use may be made of quaternary ammonium salt
- the aqueous colloidal metal solution 2 is a dispersed system composed of a metal colloid (metal particles or metal particles whose surfaces are at least partially covered with a dispersant such as citric acid) dispersed within water as the dispersion medium.
- a metal colloid metal particles or metal particles whose surfaces are at least partially covered with a dispersant such as citric acid
- the type of metal, particle diameter and shape of the metal particles may be suitably selected so as to manifest the desired function.
- metals such as gold, silver, copper, aluminum and platinum may be used, particle diameters within a range of from several nanometers to several hundreds of nanometers may be selected, and particle shapes such as a spherical or rod shape may be selected.
- the nonaqueous solvent used is a solvent which is a poor solvent for the metal colloid within the aqueous colloidal metal solution 2 , and has an excellent ability to swell the organically modified layered compound 1 .
- a solvent having a sufficiently large difference in solubility parameter (SP) with the metal colloid may be used as the nonaqueous solvent.
- the SP difference between the metal colloid and the nonaqueous solvent is preferably at least 9 MPa 1/2 , more preferably at least 13 MPa 1/2 , and even more preferably at least 21 MPa 1/2 .
- a nonaqueous solvent which is a poor solvent for the metal colloid and has an excellent ability to swell the organically modified layered compound 1 by using a nonaqueous solvent which is a poor solvent for the metal colloid and has an excellent ability to swell the organically modified layered compound 1 , it is possible to induce the formation of a composite of the organically modified layered compound 1 lipophilized by the intercalation of organic ions and the metal colloid in the aqueous colloidal metal solution 2 .
- a layered compound-metal particle composite 3 having an excellent affinity with low-polarity substances can thereby be obtained.
- the layered compound-metal particle composite 3 exhibits a high dispersion stability in nonaqueous solvents, it can be furnished in the form of suspensions (including pastes) in which a nonaqueous solvent serves as the dispersion medium.
- various functional materials can be formed using the layered compound-metal particle composite 3 or a suspension thereof.
- color materials having a high degree of durability and use as sensitized thin-films for solar cells, CCD sensors or LPR sensors based on plasmonics, and in electronic devices such as capacitors or electrode materials is also possible.
- the combination of such composites or suspensions with sensitizers and electron transporting functions similar to photosynthesis will likely lead to the creation of practical electrical storage devices and water photolysis devices which put to use the photoredox effects of these composites or suspensions.
- a suspension having the desired composite concentration (such as a paste or a dilution) can be obtained either by separating the organic phase in which the composite is dispersed from the aqueous phase, or by removing the condensed layer of composite between the aqueous phase and the organic phase and dispersing it in an organic solvent. If the composite is extracted into an organic phase, it may not be possible to obtain a suspension having a sufficient composite concentration in a single extraction operation. If this is the case, after the organic phase into which the composite has been extracted is separated from the aqueous phase, the composite can be concentrated by once again adding aqueous colloidal metal solution and causing the metal colloid to move into the organic phase. The extraction operation may be repeated as many times as needed.
- a suspension having the desired composite concentration (such as a paste or a dilution) can be obtained by dispersing in an organic solvent the composite that has settled and precipitated out.
- FIG. 2 is a diagram showing the method of producing a layered compound-metal particle composite according to the second embodiment.
- This embodiment aside from the further addition of an amphiphatic solvent differing from the nonaqueous solvent, is the same as the first embodiment.
- the explanation given below describes primarily those features of the second embodiment which differ from the first embodiment and omits those features in common with the first embodiment.
- an organically modified layered compound 1 has added thereto not only an aqueous colloidal metal solution 2 and a nonaqueous solvent, but also an amphiphatic solvent.
- the frequency of contact between the metal colloid having a high affinity with water and the organically modified layered compound 1 having a high affinity with the nonaqueous solvent is increased, making it possible to promote the formation of a composite of the metal colloid and the organically modified layered compound 1 .
- a solvent having an excellent affinity to both the water serving as the solvent in the aqueous colloidal metal solution 2 and to a nonaqueous solvent is used as the amphiphatic solvent.
- preferred use can be made of a solvent having a dielectric constant which is smaller than that of water and larger than that of the nonaqueous solvent.
- the nonaqueous solvent is acetone, ethyl acetate, toluene or the like
- methanol or ethanol may be used as the amphiphatic solvent.
- a layered compound-metal particle composite was produced as described below by a method according to the above embodiments.
- an aqueous gold nanocolloid solution was prepared as follows in accordance with a reference document (G. Frens et al., Nat. Phys. Sci . (1973)).
- 6 mL of HAuCl 4 .4H 2 O (1 wt %) was dissolved in 594 mL of ultrapure water and refluxed under heating.
- 4.92 mL of a 1 wt % aqueous solution of trisodium citrate was added and refluxing was continued.
- the solution changed in color from light-yellow to red.
- refluxing was stopped and the solution was allowed to cool naturally, following which it was stored under darkened conditions at room temperature.
- the transmission/absorption spectrum of the aqueous gold nanocolloid solution thus obtained was measured, yielding the results shown in FIG. 3 . Because the plasmon absorption according to the transmission/absorption spectrum measured was 534 nm, the diameter of the gold nanoparticles was assumed to be about 55 to 60 nm.
- the aqueous phase at this time was red, whereas the organic phase was clear.
- This liquid was vigorously stirred for 30 seconds and left at rest for 10 minutes, whereupon the organic phase became red in color and the aqueous phase became clear (right-hand vial in FIG. 4 ). From the change in the colors of the respective phases, even though the amount of solvent was smaller in the organic phase (10 mL) than in the aqueous phase (50 mL), it was confirmed that, due to stirring following addition of the aqueous gold nanocolloid solution in the presence of ethyl acetate, most of the gold colloid moved from the aqueous phase to the organic phase.
- the organic phase was separated from the liquid ultimately obtained (right-hand vial in FIG. 4 ), and the solvent was removed by distillation, whereupon a red-violet residue was recovered.
- the FT-IR spectrum of this red-violet residue was measured, giving the results shown in FIG. 5 . From the FT-IR measurement results for the red-violet residues, —OH stretching absorption from smectite was observed near 3320 cm ⁇ 1 . Hence, the above red-violet residue was confirmed to be a composite of gold nanoparticles and smectite.
- a gold nanocolloid solution was prepared by the same procedure as in Example 1.
- the transmission/absorption spectrum of this gold nanocolloid solution was measured, whereupon the plasmon absorption was 520 nm, based on which the diameter of the gold nanoparticles was assumed to be about 20 nm.
- the diameter of the particles was 20 ⁇ 2 nm.
- Example 1 Using this gold nanocolloid solution, a liquid that separated into an aqueous phase and an organic phase was obtained by the same procedure as in Example 1. As in Example 1, movement of the gold nanoparticles from the aqueous phase into the organic phase was confirmed at this time, and the color of the final organic phase was red-violet.
- Lipophilized synthetic smectite SAN available from CO-OP CHEMICAL CO., LTD. was dissolved in 10 mL of toluene to prepare a toluene solution having a smectite concentration of 0.05 wt %, and a uniform dispersion of fine particles was obtained by ultrasonic irradiation.
- 50 mL of the same aqueous gold colloid solution as in Example 2 was added to this dispersion and extraction operations like those in Example 2 were carried out, giving a red organic phase.
- the operations of discarding the substantially colorless aqueous phase, freshly adding 50 mL of aqueous gold colloid solution and again extracting were repeated seven times, thereby concentrating the gold colloid in the organic phase.
- the concentrate was then held for 3 hours on a hot plate at 100° C. or above, thereby removing moisture from organic phase and giving a highly viscous red paste.
- To this paste was added 3 mL of a 0.1 g/L solution of polymethyl methacrylate (PMMA, from Aldrich Co.; number-average molecular weight, 44,700).
- PMMA polymethyl methacrylate
- the mixture was kneaded for a full day on a roll mill, after which it was coated onto a base film using a doctor blade, left to stand for 1 hour in a 100° C. oven to remove the solvent, then peeled from the base film, giving a transparent, blue-tinged film having a thickness of about 0.4 ⁇ m and measuring about 10 cm square in size.
- the transparent film was transferred onto a glass plate and the surface resistance was measured with a four-point probe, yielding a value of 50 ⁇ /. This showed that the film can be used as a polarizable (dielectric) electrode.
- aqueous silver nanocolloid solution was prepared as follows in accordance with a reference document (P. C. Lee et al, J. Phys. Chem. B (1982)). Next, 54 mg of AgNO 3 was dissolved in 300 mL of water, giving a colorless liquid. This was refluxed and boiled under degassing. Next, 6 mL of a 10 wt % aqueous solution of trisodium citrate was added. Several minutes later, the solution had turned yellow; after 15 to 20 minutes, the color of the solution turned yellowish-gray.
- aqueous silver colloid solution (30 mL) was added to 2.5 mL of a 1 wt % acetone solution of lipophilized synthetic smectite STN available from CO-OP CHEMICAL CO., LTD., and a greenish-brown precipitate at once settled out.
- the precipitate was collected by filtration, washed with methanol and dried at room temperature, following which it was ultrasonically dispersed in ⁇ -butyrolactone. This dispersion appeared green in color but was clear; no precipitation occurred even after 2 months of standing.
- Example 5 Aside from the use, as the smectite, of the hydrophilic smectite SWN (from CO-OP CHEMICAL CO., LTD.) that had not been subjected to lipophilizing treatment, the experiment was carried out under the same conditions as in Example 5. No change whatsoever was observed in the aqueous silver colloid solution; a stable dispersed state was maintained. This showed that the settling out of the greenish-brown precipitate in Example 5 was brought about by lipophilizing treatment of the smectite.
- SWN hydrophilic smectite SWN
- the FT-IR spectrum of this colored powder was measured and compared with the FT-IR spectrum for the smectite SAN alone. As shown in FIG. 9 , both had peaks at substantially the same wavenumbers. This showed that the colored powder was a composite of the lipophilized smectite and the silver colloid particles.
- a 10 ⁇ 4 mol/L ethanol solution of the coumarin-type cationic dye 7-N,N-dimethylamino-4-methylcoumarin (Coumarin 311, from Aldrich Co.; laser-grade) was prepared, an aqueous dispersion of montmorillonite (trade name, Kunipia F; from KUNIMINE INDUSTRIES CO., LTD.) was added to the solution, and the colored precipitate that formed was recovered. This colored precipitate was dried, then adjusted to a solids content of 10 wt % in acetone, and fine particle dispersion was carried out for 1 hour in a sand mill using 0.3 mm diameter zirconia particles as the grinding media.
- montmorillonite trade name, Kunipia F; from KUNIMINE INDUSTRIES CO., LTD.
- Example 5 When the aqueous silver nanocolloid solution prepared in Example 5 was added dropwise to the resulting dispersion, a greenish-gray precipitate formed at once. This colored precipitate was collected, following which it was subjected, as a mixture of the weight composition indicated below, to roll mill treatment for a full day, yielding a beige-colored paste.
- Silver nanocolloid-coumarin dye-modified 125 parts by weight montmorillonite composite Azobisisobutyronitrile 3 parts by weight Polyvinyl butyrate resin (Sekisui Chemical 25 parts by weight Co., Ltd.) Ethyl acetate 100 parts by weight
- This paste was applied with a doctor blade onto a 100 ⁇ m thick polyethylene terephthalate (PET) film, then dried under heating at 100° C. for 5 minutes, giving a laminated film composed of a 1 ⁇ m thick light yellow-green cloudy layer formed on a base film.
- the total light transmittance of this thin-film, including the base film, was 47%.
- this cloudy layer was laid on top of the anti-reflective coating of a silicon photodiode (S2386-18K, from HAMAMATSU PHOTONICS K.K.) and pressed under applied heat at 60° C. for 3 minutes, following which the base film was peeled off, forming a laminating layer on the photodiode.
- photocurrent enhancement ratio The ratio with respect to the photocurrent of a silicon photodiode to which lamination had not been carried out. Transfer of the laminating layer onto the photodiode resulted in a photocurrent that was 1.5 times larger.
- IPCE incidence photon to current efficiency
- the Ag-lipophilized smectite composite prepared in Example 6 was added to a mixed solution of PCBM and P3HT (solvent, chlorobenzene) in a ratio of 10 wt % with respect to the solids content of the latter, and ball mill dispersion was carried out.
- an aqueous solution of PEDOT:PSS was spin-coated onto the transparent electrode side of an ITO/glass substrate and dried, forming a p-type conductive polymer film (hole-transporting layer).
- the dispersion of Ag-lipophilized smectite composite, PCBM and P3HT prepared above was spin-coated onto this p-type conductive polymer, thereby forming a photoelectric conversion layer.
- an aluminum electrode was formed on the surface layer by vacuum vapor deposition, giving an organic solar cell sample.
- IPCE of this organic solar cell sample was measured. On comparing the IPCE values both in the presence and absence of a Ag-smectite composite nanoparticle layer, it was found that providing a composite particle layer increased the IPCE 1.5-fold.
- Example 10 Aside from not including lipophilized smectite SAN, the same exact procedure was carried out as in Example 10. In contrast with Example 10, no metal colloid whatsoever aggregated at the interface between the aqueous phase and the organic phase. The aqueous phase continued to exhibit the red color characteristic of the colloid, and the organic phase continued to be colorless. It is apparent from this that the aggregation of metal colloid at the interface which occurred in Example 10 was brought about by the addition of a small amount of lipophilized clay to the organic phase.
- the electrical double-layer capacitor 10 has a construction in which the separator 18 is positioned between current-collecting electrode films 16 , each of which is composed of a PMMA resin 12 and a gold current-collecting electrode 14 .
- Example 5 20 mL of the aqueous silver colloid solution shown in Example 5 was placed in a 50 mL screw-top vial. Next, a solution obtained by adding 5 ⁇ L of a dispersion containing 1 wt % of lipophilized synthetic smectite SAN (trade name; from CO-OP CHEMICAL CO., LTD.) to 3 mL of a toluene solution and dispersing the fine particles was added. The resulting mixture was vigorously shaken and left at rest, whereupon an interface having a golden luster formed between the aqueous phase and the organic phase.
- a dispersion containing 1 wt % of lipophilized synthetic smectite SAN trade name; from CO-OP CHEMICAL CO., LTD.
- the scale was increased 50-fold and, in terms of volume, about 0.5 mL of interfacial metal film was collected from 1 liter of aqueous silver colloid solution by carrying out the same operations as above.
- This metal film was ultrasonically dispersed for 1 hour in 5 mL of a water-methanol (volume ratio, 1:7) mixed solvent, giving a green paste.
- this paste was applied while wet onto a glass substrate to a thickness of about 5 ⁇ m, and hot-air dried at 100° C., yielding a lustrous film that was greenish-gray in appearance and had transparency.
- the surface resistance of the film was about 5 ⁇ /cm.
- a 35 wt % ethanol solution of lipophilized synthetic smectite SPN (trade name; CO-OP CHEMICAL CO., LTD.) was impregnated into a cellulose-based Millipore filter having a thickness of 90 ⁇ m and dried 2 hours at room temperature, thereby supporting the lipophilized clay and giving an insulating layer.
- BN composite resin HIBORON BN-2, from Boron International Co., Ltd.
- a mixed layer of BN-composite resin (HIBORON BN-2) and Ag-smectite composite which contained none of the compound having photoredox properties was formed to the same thickness on the opposite side of the insulating layer, thereby forming a dielectric layer.
- the resistance in the thickness direction was 20 k ⁇ .
- Blue-colored films (Au current-collecting electrode films) produced by the method described in Example 10 were stacked onto both sides of this dielectric layer, thereby creating the photocapacitor having a 5-layer structure shown schematically in FIG. 11 .
- the photocapacitor 20 is composed of, as successive layers from the light input side, a current-collecting electrode film 16 , a photodielectric layer 22 , an insulating layer 24 , a dielectric layer 26 , and a current-collecting electrode film 16 .
- a photocurrent of about 1 ⁇ A/cm 2 was momentarily observed, creating a photovoltaic power of about 0.2 V between both electrodes. Even when light irradiation was stopped, the potential was retained for at least 24 hours. Only when connected to an external circuit did the potential fall to 0.
- a thick paste was prepared by using a roll mill to knead the Ag-smectite composite obtained in Example 6 into a methyl ethyl ketone solution containing 70 wt % of BN-4 (a BN composite resin in the form of a solid) to a solids content of 30 wt %.
- BN-4 a BN composite resin in the form of a solid
- Example 12 the transparent electrode film shown in Example 12 was laminated onto the side opposite from the aluminum foil and bonded under heat and pressure at 150° C., thereby giving a film-type solar cell having greater flexibility and a thickness on the order of several microns.
- the resistance value between both electrodes at room temperature was about 1 M ⁇ .
- FIG. 12 is a diagram showing the structure of the film-type solar cell produced in Example 14.
- the solar cell 30 has a structure composed of, as successive layers from the light input side, a silver current-conducting electrode (the transparent electrode film of Example 12) 32, a solid electrolyte membrane 34 impregnated with a paste containing the composite of Example 6, and aluminum foil 36 .
- a uniform slurry solution was prepared by mixing together 10 wt % of the hydrophilic clay SWN(CO-OP CHEMICAL CO., LTD.), 3 wt % of a crosslinking agent (HIBORON B-1; Boron International Co., Ltd.) and 2 wt % of polyvinyl alcohol.
- a separator for use in capacitors was immersed for 15 minutes at room temperature in this slurry solution, then drawn out and hot-air dried.
- This paper-based ion-exchange material was again immersed for 1 hour in a 50 mM methyl viologen solution, then drawn out, washed with a copious amount of water and dried, thereby fixing the bipyridinium skeleton within the clay (solid electrolyte) by ion exchange.
- the current-collecting electrode film of Example 12 was immersed for a full day in a THF solution containing 5 mM of the dyes mentioned below and thereby made to adsorb the dyes, following which the film was drawn out, excess dye was washed away with a copious amount of ethanol, and the film was bonded under heat (150° C.) and pressure to one side of the above porous layer-clay-viologen composite paper.
- the photolytic device 40 shown in this diagram has a structure composed of, as successive layers, a silver current-collecting electrode (anode) 32 to which a dye (Dye 1) has been adsorbed, a solid electrolyte 42 in which methyl viologen has been fixed, and a platinum electrode (cathode) 44 containing the compound ZnP(6)V (Dye 2) having photoredox properties.
- This photolytic device was placed at the center of a reaction cell having the structure (half) shown in FIG. 14 , and water tanks on both sides were filled with distilled water. Next, both sides of the composite film at the center were irradiated with Xe light. Bubbles began forming at the interface between the film and water immediately after the start of irradiation, the amount of bubbles generated increasing with the passage of time. The gas that evolved was collected in a collection bottle and analyzed by gas chromatography, from which it was determined that oxygen formed on the Au electrode side and hydrogen formed on the Pt electrode side.
- FIG. 17 is a table showing the relationship between the composite formation conditions and the composite forming phenomena for the working examples and comparative examples in which layered compound-metal particles composites were produced.
- Examples 1 to 8, 10 and 12 an organically modified layered compound lipophilized by the intercalation of organic ions was used, and a nonaqueous solvent which is a poor solvent for a metal colloid and has an excellent ability to swell the organically modified layered compound was added together with an aqueous colloidal metal solution. As a result, the formation of a composite of the organically modified layered compound and the metal colloid proceeded, giving a layered compound-metal particle composite.
- the difference in solubility parameter (SP) between the metal colloid and the nonaqueous solvent was at least 21 MPa 1/2 . The method used to calculate the difference in SP values is described later.
- these cases divide into, depending on the nonaqueous solvent added, cases in which there arises phase separation into an organic phase that stably disperses a large amount of composite and an aqueous phase that contains substantially no composite (Examples 1 to 4, 10 and 12), and cases in which the composite settles out and precipitates in a state where all the solvents are uniformly compatible.
- the former case because a suspension of the composite stably dispersed in the nonaqueous solvent making up the organic phase is directly obtained, the subsequent process (following dispersion of the composite in the organic solvent, a functional film is formed by coating) is simplified, which is efficient.
- the method of calculating the “SP difference” in FIG. 17 is explained here.
- the SP values (MPa 1/2 ) for nonaqueous solvents used were 18.6 for ethyl acetate, 18.2 for toluene, and 20.3 for acetone.
- the solubility parameters of metal colloids in aqueous colloidal metal solutions were calculated from their solubilities in reference solvents (water, ethanol, methanol) by the procedure shown below and based on the following assumptions.
- the solubility in water of the dispersant trisodium citrate dihydrate is 720 g/L (25° C.), from which the solubility at laboratory temperature (16° C.) was estimated to be 500 g/L. Moreover, it was confirmed that 500 g of trisodium citrate dihydrate dissolves completely in 1 liter of water.
- mixed solvents were prepared by mixing together water and methanol in a mixing ratio (water:methanol) of 9:1 (Mixed Solvent 3), or in a mixing ratio (water:methanol) of 8:2 (Mixed Solvent 4).
- trisodium citrate dihydrate was dissolved in these Mixed Solvents 3 and 4 to a concentration of 500 g/L. As a result, all of the trisodium citrate dihydrate dissolved in Mixed Solvent 3, whereas a small portion precipitated in Mixed Solvent 4.
- solubility parameters for trisodium citrate were estimated as follows from the known solubility parameters of water, ethanol and methanol.
- the solubility parameters used for water, ethanol and methanol were respectively 47.9 MPa 1/2 , 26.0 MPa 1/2 and 29.7 MPa 1/2 .
- the SP of trisodium citrate i.e., the SP of the metal colloid, was then obtained as the average of the SP estimated by the ethanol method (45.7) and the SP estimated by the methanol method (44.3), or 45.0 MPa 1/2 .
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Abstract
Description
Silver nanocolloid-coumarin dye-modified | 125 parts by weight | ||
| |||
Azobisisobutyronitrile | |||
3 parts by weight | |||
Polyvinyl butyrate resin (Sekisui Chemical | 25 parts by weight | ||
Co., Ltd.) | |||
Ethyl acetate | 100 parts by weight | ||
- Assumption 1: The solubility parameters for the metal colloids are the same as the solubility parameter for trisodium citrate, which is a surface modifier (dispersant).
- Assumption 2: The solubility parameters have additivity.
SP for trisodium citrate=0.9×(SP of water)+0.1×(SP of ethanol)=45.7
SP for trisodium citrate=0.8×(SP of water)+0.2×(SP of methanol)=44.3
Claims (20)
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PCT/JP2012/053341 WO2012111647A1 (en) | 2011-02-14 | 2012-02-14 | Layered compound-metal particle composite and production method therefor, and suspension, film and flexible solar cell using same |
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WO2016035109A1 (en) * | 2014-09-05 | 2016-03-10 | 西松建設株式会社 | Composite containing silver nanoparticles and antibacterial agent, photoelectric converter, photosensitive pointing device, and thin-film photovoltaic cell using this composite |
JP6080233B2 (en) * | 2015-07-17 | 2017-02-15 | 西松建設株式会社 | Functional light transmitting material and manufacturing method thereof |
JP2017156104A (en) * | 2016-02-29 | 2017-09-07 | 西松建設株式会社 | Light enhancement element, manufacturing method of the same, and spectroanalysis kit and spectroanalysis method |
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CN110586956A (en) * | 2019-09-29 | 2019-12-20 | 同济大学 | Method for in-situ synthesis of montmorillonite/gold nanorod composite material |
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US20140076384A1 (en) | 2014-03-20 |
KR101934376B1 (en) | 2019-01-02 |
JP5820592B2 (en) | 2015-11-24 |
EP2676931A1 (en) | 2013-12-25 |
EP2676931B1 (en) | 2019-09-18 |
CN103502148A (en) | 2014-01-08 |
KR20140045921A (en) | 2014-04-17 |
DK2676931T3 (en) | 2019-12-02 |
JP2012166145A (en) | 2012-09-06 |
EP2676931A4 (en) | 2017-08-16 |
CN103502148B (en) | 2015-07-22 |
WO2012111647A1 (en) | 2012-08-23 |
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